A theoretical study on the hydrogenation of CO<sub>2</sub>to methanol catalyzed by ruthenium pincer complexes

Zhou, Ying; Zhao, Yaqi; Shi, Xiaofan; Tang, Yanhui; Yang, Zixu; Pu, Min; Lei, Ming

doi:10.1039/d2dt01352e

Cited by 12 publications

(14 citation statements)

References 55 publications

(70 reference statements)

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“…Three cascade cycles were proposed: hydrogenation of CO 2 to HCOOH, hydrogenation of HCOOH to methanediol which decomposes to HCHO and water, and hydrogenation of HCHO to CH 3 OH. A similar mechanism was proposed by Lei and co‐workers for CO 2 hydrogenation catalyzed by a Mn pincer complex, Mn(Ph 2 PCH 2 SiMe 2 ) 2 N(CO) 2 , or a Ru pincer complex, RuH 2 (Me 2 PCH 2 SiMe 2 ) 2 NH(CO) [45, 46] . Here, H 2 activation is the rate‐controlling step in each catalytic cycle under solvent‐free conditions.…”

Section: Chemical Catalysissupporting

confidence: 57%

“…A similar mechanism was proposed by Lei and co‐workers for CO 2 hydrogenation catalyzed by a Mn pincer complex, Mn(Ph 2 PCH 2 SiMe 2 ) 2 N(CO) 2 , or a Ru pincer complex, RuH 2 (Me 2 PCH 2 SiMe 2 ) 2 NH(CO). [ 45 , 46 ] Here, H 2 activation is the rate‐controlling step in each catalytic cycle under solvent‐free conditions. In comparison, the reaction is more favorable in the appropriate solvent (water, toluene, THF) than in the gas phase.…”

Section: Chemical Catalysismentioning

confidence: 99%

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Challenges and Prospects in the Catalytic Conversion of Carbon Dioxide to Formaldehyde

et al. 2022

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Formaldehyde (HCHO) is a crucial C1 building block for daily‐life commodities in a wide range of industrial processes. Industrial production of HCHO today is based on energy‐ and cost‐intensive gas‐phase catalytic oxidation of methanol, which calls for exploring other and more sustainable ways of carrying out this process. Utilization of carbon dioxide (CO2) as precursor presents a promising strategy to simultaneously mitigate the carbon footprint and alleviate environmental issues. This Minireview summarizes recent progress in CO2‐to‐HCHO conversion using hydrogenation, hydroboration/hydrosilylation as well as photochemical, electrochemical, photoelectrochemical, and enzymatic approaches. The active species, reaction intermediates, and mechanistic pathways are discussed to deepen the understanding of HCHO selectivity issues. Finally, shortcomings and prospects of the various strategies for sustainable reduction of CO2 to HCHO are discussed.

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Section: Chemical Catalysissupporting

confidence: 57%

Section: Chemical Catalysismentioning

confidence: 99%

Challenges and Prospects in the Catalytic Conversion of Carbon Dioxide to Formaldehyde

et al. 2022

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“…Transition metal catalysts are widely used in organic synthesis. − To evaluate the efficacy of the i-EIP method for transition metal-catalyzed reactions, five reactions were selected from a variety of published libraries − for use as a test set. The selected reactions contain different transition metal atoms, and the size of these reaction systems is relatively large.…”

Section: Resultsmentioning

confidence: 99%

Improved Elastic Image Pair Method for Finding Transition States

Liu

Lei

2023

J. Chem. Theory Comput.

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The elastic image pair (EIP) method is a robust method for finding approximate transition states between two local minima. However, the original implementation of the method had some limitations. In this work, we present an improved EIP method, in which the moving procedure of the image pair and the convergence strategy are modified. In addition, this method is combined with the rational function optimization method to give exact transition states. Tests on a set of 45 different reactions show the reliability and efficiency in finding transition states.

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“…Being consistent with our previous research on the mechanisms of hydrogenation reaction catalyzed by transition-metal complexes [ 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 ], all the calculations were performed using the ωB97X-D/BSI method employing the Gaussian 09 program [ 25 , 26 ]. BSI indicates that the LANL2DZ basis set was used for Ir atom and 6-31G* basis set for all other non-metal atoms [ 27 , 28 , 29 ].…”

Section: Methodsmentioning

confidence: 99%

The Origin of Stereoselectivity in the Hydrogenation of Oximes Catalyzed by Iridium Complexes: A DFT Mechanistic Study

et al. 2022

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Herein the reaction mechanism and the origin of stereoselectivity of asymmetric hydrogenation of oximes to hydroxylamines catalyzed by the cyclometalated iridium (III) complexes with chiral substituted single cyclopentadienyl ligands (Ir catalysts A1 and B1) under acidic condition were unveiled using DFT calculations. The catalytic cycle for this reaction consists of the dihydrogen activation step and the hydride transfer step. The calculated results indicate that the hydride transfer step is the chirality-determining step and the involvement of methanesulfonate anion (MsO−) in this reaction is of importance in the asymmetric hydrogenation of oximes catalyzed by A1 and B1. The calculated energy barriers for the hydride transfer steps without an MsO− anion are higher than those with an MsO− anion. The differences in Gibbs free energies between TSA5−1fR/TSA5−1fS and TSB5−1fR/TSB5−1fS are 13.8/13.2 (ΔΔG‡ = 0.6 kcal/mol) and 7.5/5.6 (ΔΔG‡ = 1.9 kcal/mol) kcal/mol for the hydride transfer step of substrate protonated oximes with E configuration (E−2a−H+) with MsO− anion to chiral hydroxylamines product R−3a/S−3a catalyzed by A1 and B1, respectively. According to the Curtin–Hammet principle, the major products are hydroxylamines S−3a for the reaction catalyzed by A1 and B1, which agrees well with the experimental results. This is due to the non-covalent interactions among the protonated substrate, MsO− anion and catalytic species. The hydrogen bond could not only stabilize the catalytic species, but also change the preference of stereoselectivity of this reaction.

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A theoretical study on the hydrogenation of CO₂to methanol catalyzed by ruthenium pincer complexes

Abstract: Herein, a density functional theory (DFT) study was performed to investigate thoroughly the cascade reaction mechanism for the hydrogenation of carbon dioxide to methanol catalyzed by ruthenium pincer complex [RuH2(Me2PCH2SiMe2)2NH(CO)]....

Cited by 12 publications

References 55 publications

Challenges and Prospects in the Catalytic Conversion of Carbon Dioxide to Formaldehyde

Challenges and Prospects in the Catalytic Conversion of Carbon Dioxide to Formaldehyde

Improved Elastic Image Pair Method for Finding Transition States

The Origin of Stereoselectivity in the Hydrogenation of Oximes Catalyzed by Iridium Complexes: A DFT Mechanistic Study

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A theoretical study on the hydrogenation of CO2to methanol catalyzed by ruthenium pincer complexes

Abstract: Herein, a density functional theory (DFT) study was performed to investigate thoroughly the cascade reaction mechanism for the hydrogenation of carbon dioxide to methanol catalyzed by ruthenium pincer complex [RuH2(Me2PCH2SiMe2)2NH(CO)]....

Cited by 12 publications

References 55 publications

Challenges and Prospects in the Catalytic Conversion of Carbon Dioxide to Formaldehyde

Challenges and Prospects in the Catalytic Conversion of Carbon Dioxide to Formaldehyde

Improved Elastic Image Pair Method for Finding Transition States

The Origin of Stereoselectivity in the Hydrogenation of Oximes Catalyzed by Iridium Complexes: A DFT Mechanistic Study

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A theoretical study on the hydrogenation of CO₂to methanol catalyzed by ruthenium pincer complexes